CN104371076B - A kind of method of normal temperature synthesis polycarboxylate water-reducer - Google Patents

A kind of method of normal temperature synthesis polycarboxylate water-reducer Download PDF

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CN104371076B
CN104371076B CN201410726526.8A CN201410726526A CN104371076B CN 104371076 B CN104371076 B CN 104371076B CN 201410726526 A CN201410726526 A CN 201410726526A CN 104371076 B CN104371076 B CN 104371076B
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normal temperature
liquid
polycarboxylate water
water
temperature synthesis
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CN104371076A (en
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孟祥娣
杨晓
郭晓磊
高勇利
苏亚楠
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Hebei Tieyuan Science & Technology Development Co Ltd
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Hebei Tieyuan Science & Technology Development Co Ltd
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Abstract

The invention discloses a kind of method of normal temperature synthesis polycarboxylate water-reducer, preparation method comprises the following steps:1) under normal temperature, unsaturated APEO and water are added into reactor stirring;2) while A liquid and B liquid is added dropwise, A liquid is unsaturated carboxylic acid or acid anhydrides, the mixed aqueous solution of reducing agent and chain-transferring agent, and time for adding is 3 3.5h, and B liquid is aqueous oxidizing agent solution, and time for adding is 2 2.5h;3) curing 1h is dripped, adds sodium hydroxide solution, adjustment pH value to 57.The polycarboxylate water-reducer of the present invention is obtained using water as solvent by radical polymerization at normal temperatures.Whole building-up process saves the energy, reduces pollution, and water-reducing property is better than domestic and international product, can widely apply in the industrial production without heating.

Description

A kind of method of normal temperature synthesis polycarboxylate water-reducer
Technical field
The present invention relates to a kind of method of normal temperature synthesis polycarboxylate water-reducer, belong to technical field of concrete additives.
Background technology
In construction material, concrete is that dosage is maximum and most widely used, and as the poly- of concrete BSA The advantages that carboxylic acid high-performance water reducing agent is because its dispersive property is good, water-reducing rate height, and plasticity is good is paid close attention to by academia, and near Promoted rapidly in year a bit, applied to the Important Project such as railway, highway, bridge, tunnel, water power, harbour, airport, harbour, civilian In.
With the continuous consumption of non-renewable energy resources, the earth will face lack of energy.Usual poly carboxylic acid series water reducer Synthesis, which needs to be heated at high temperature, can just obtain, complex process, while the requirement to consersion unit is also high, how to reduce polycarboxylic-acid and subtracts Energy resource consumption in aqua synthesis turns into the major issue that polycarboxylic acids synthesis faces.
The content of the invention
The technical problem to be solved in the present invention is, there is provided one kind synthesizes high performance polycarboxylate water-reducer at normal temperatures Method, reduce energy resource consumption, improve active constituent content, and it is applied to industrial production.
The present invention solve the technical scheme that uses of its technical problem for:
A kind of method of normal temperature synthesis polycarboxylate water-reducer, its raw material include the component of following mass fraction:Unsaturation is poly- 100 parts of oxygen vinethene polymeric monomer, unsaturated carboxylic acid or anhydrides monomer 5-18 parts, oxidant 0.5-3 parts, reducing agent 0.01-0.3 Part, chain-transferring agent 0.05-0.8 parts, sodium hydroxide 1-5 parts.
Further, it comprises the following steps:
Step 1)At 25 DEG C -35 DEG C, by unsaturated APEO polymeric monomer and water with mass ratio 1:3 add reaction Kettle, stirred with 85-95r/min;
A liquid and B liquid is added dropwise while stirring in step 2), and A liquid is the unsaturated carboxylic acid or acid anhydrides, reducing agent and chain The mixed aqueous solution of transfer agent, time for adding 3-3.5h, 30-50mL being uniformly added dropwise per hour, B liquid is aqueous oxidizing agent solution, Time for adding is 2-2.5h, and 20-30mL is uniformly added dropwise per hour;
Step 3) drips, and cures 1h, adds sodium hydroxide solution, adjustment pH value to 5-7.
Preferably, the unsaturated APEO polymeric monomer is methyl allyl polyoxyethylene ether or prenol polyoxy Vinethene.
Preferably, the unsaturated APEO polymeric monomer degree of unsaturation is more than 0.37, weight average molecular weight 2400.
Preferably, the unsaturated carboxylic acid or acid anhydrides are at least one of acrylic acid, methacrylic acid or maleic anhydride.
Preferably, the oxidant be potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide or permanganic acid in extremely Few one kind.
Preferably, the reducing agent be vitamin C, ferrous sulfate, sodium hypophosphite, oxalic acid or sodium thiosulfate in extremely Few one kind.
Preferably, the chain-transferring agent is TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids or methallylsulfonic acid sodium At least one of.
Preferably, the sodium hydroxide solution use mass concentration for 40% sodium hydrate aqueous solution.
The present invention is beneficial to be had the technical effect that:Present invention synthesis polycarboxylate water-reducer uses dropwise addition mode, big single before dropwise addition Body need not all dissolve, and dissolved when being added dropwise, save the dissolution time of monomer, save the material time;Using being synthesized under normal temperature, Whole building-up process saves the energy, no noxious emission, does not pollute the environment, can be widely used in industrial production without heating. The polycarboxylate water-reducer water-reducing rate of this method synthesis is high, hence it is evident that better than like product.
Embodiment
In order that the technological means and operating process of the present invention are simple and clear, done further with reference to specific embodiment Illustrate.
Embodiment 1:
The methyl allyl polyoxyethylene ether 360g and 270g of molecular weight 2400 water are added in four-hole bottle and stirred 20min.39g acrylic acid, 1.31g TGAs and 0.54g vitamin Cs are dissolved in 86g water, it is well mixed to obtain A liquid.Will 4.88g hydrogen peroxide and 52g water is mixed to get B liquid.A liquid and B liquid is added dropwise simultaneously, wherein A drops add 3h, and B drops add 2h, are added dropwise Process is without heating.After being added dropwise, 1h is cured, the sodium hydroxide solution of 13g mass fractions 40% is added afterwards, adds running water All solutes are adjusted in solution relative to the mass concentration of water to 40%, that is, obtain the poly carboxylic acid series water reducer of embodiment 1.
Embodiment 2:
The methyl allyl polyoxyethylene ether 360g and 270g of molecular weight 2400 water are added in four-hole bottle and stirred 20min.42g methacrylic acids, 1.40g TGAs and 0.60g vitamin Cs are dissolved in 86g water, it is well mixed to obtain A Liquid.5.04g hydrogen peroxide and 52g water are mixed to get B liquid.A liquid and B liquid is added dropwise simultaneously, wherein A drops add 3.5h, and B drops add 2h, process is added dropwise without heating.After being added dropwise, 1h is cured, the sodium hydroxide solution of 14g mass fractions 40% is added afterwards, adds In running water adjustment solution all solutes obtain poly carboxylic acid series water reducer of the invention relative to the mass concentration of water to 40%.
Embodiment 3:
The isoamyl alcohol polyoxyethylene ether 360g and 270g of molecular weight 2400 water are added in four-hole bottle and stir 20min. 43g acrylic acid, 1.59g mercaptopropionic acids and 0.66g vitamin Cs are dissolved in 86g water, it is well mixed to obtain A liquid.By 4.92g Hydrogen peroxide and 52g water be mixed to get B liquid.A liquid and B liquid is added dropwise simultaneously, wherein A drops add 3h, and B drops add 2.5h, were added dropwise Cheng Wuxu is heated.After being added dropwise, 1h is cured, the sodium hydroxide solution of 14g mass fractions 40% is added afterwards, adds running water to adjust In whole solution all solutes obtain poly carboxylic acid series water reducer mother liquor of the invention relative to the mass concentration of water to 40%.
Embodiment 4-12
Embodiment 4-12 is to select component and parts by weight such as table 1 to match with embodiment difference.
The embodiment 4-12 of table 1 component and proportioning
The present invention also can be selected can in the unsaturated carboxylic acid or anhydrides monomer, oxidant, reducing agent and chain-transferring agent Any independent assortment of component is selected, gross mass number meets present invention limitation.
Obtained water reducer in above-described embodiment 1-3 and the water reducer of comparative example 1 and 2 are subjected to performance comparison, experiment uses The prosperous cement of P.O42.5 ancient cooking vessels and P.O42.5 Jis east cement carry out net slurry detection to obtained water reducer, and detection method is referring to GB- 8077-2010, specific net slurry flow-data are shown in Table 2.
Comparative example 1 is identical with the raw material of embodiment 1, the difference is that only that while stirring, A liquid and B is added dropwise in step 2) Liquid, A liquid is the unsaturated carboxylic acid or acid anhydrides, the mixed aqueous solution of reducing agent and chain-transferring agent, time for adding 1h, per hour 100mL is uniformly added dropwise, B liquid is aqueous oxidizing agent solution, time for adding 0.5h, 100mL is uniformly added dropwise per hour.
Comparative example 2 is identical with the raw material of embodiment 2, the difference is that only that while stirring, A liquid and B is added dropwise in step 2) Liquid, A liquid is the unsaturated carboxylic acid or acid anhydrides, the mixed aqueous solution of reducing agent and chain-transferring agent, time for adding 1h, per hour 100mL is uniformly added dropwise, B liquid is aqueous oxidizing agent solution, time for adding 0.5h, 100mL is uniformly added dropwise per hour.
The flowing degree of net paste of cement of table 2
Find out from the flowing degree of net paste of cement experimental result of table 2, the diminishing effect of polycarboxylate water-reducer prepared by 3 example normal temperature Fruit is preferable, can carry out industrialized production and application.
The present invention is not limited to the above embodiments, simply illustrates the present invention described in above-described embodiment and specification Principle, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, and these change and changed Enter all fall within the protetion scope of the claimed invention.

Claims (8)

  1. A kind of 1. method of normal temperature synthesis polycarboxylate water-reducer, it is characterised in that its raw material includes the component of following mass fraction: Unsaturated 100 parts of APEO polymeric monomer, unsaturated carboxylic acid or anhydrides monomer 5-18 parts, oxidant 0.5-3 parts, reducing agent 0.01-0.3 parts, chain-transferring agent 0.05-0.8 parts, sodium hydroxide 1-5 parts;
    Preparation technology specifically comprises the following steps:
    Step 1)At 25 DEG C -35 DEG C, by unsaturated APEO polymeric monomer and water with mass ratio 1:3 add reactor, stir Mix;
    A liquid and B liquid is added dropwise while stirring in step 2), and A liquid is the unsaturated carboxylic acid or acid anhydrides, reducing agent and chain tra nsfer The mixed aqueous solution of agent, time for adding 3-3.5h, 30-50mL is uniformly added dropwise per hour, B liquid is aqueous oxidizing agent solution, is added dropwise Time is 2-2.5h, and 20-30mL is uniformly added dropwise per hour;
    Step 3) drips, and cures 1h, adds sodium hydroxide solution, adjustment pH value to 5-7.
  2. A kind of 2. method of normal temperature synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that the unsaturation APEO polymeric monomer is methyl alkenyl APEO or isoamyl alcohol polyoxyethylene ether.
  3. A kind of 3. method of normal temperature synthesis polycarboxylate water-reducer according to claim 2, it is characterised in that the unsaturation APEO polymeric monomer degree of unsaturation is more than 0.37, weight average molecular weight 2400.
  4. A kind of 4. method of normal temperature synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that the unsaturation Carboxylic acid or acid anhydrides are at least one of acrylic acid, methacrylic acid or maleic anhydride.
  5. A kind of 5. method of normal temperature synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that the oxidant For at least one of potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide or permanganic acid.
  6. A kind of 6. method of normal temperature synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that the reducing agent For at least one of vitamin C, ferrous sulfate, sodium hypophosphite, oxalic acid or sodium thiosulfate.
  7. A kind of 7. method of normal temperature synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that the chain tra nsfer Agent is at least one of TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids or methallylsulfonic acid sodium.
  8. A kind of 8. method of normal temperature synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that the hydroxide Sodium solution use mass concentration for 40% sodium hydrate aqueous solution.
CN201410726526.8A 2014-12-04 2014-12-04 A kind of method of normal temperature synthesis polycarboxylate water-reducer Expired - Fee Related CN104371076B (en)

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CN106145747A (en) * 2015-04-24 2016-11-23 北京麦凯特科技有限公司 A kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof
CN104987469A (en) * 2015-06-30 2015-10-21 同济大学 Preparing method for high dispersion type polycarboxylate water reducing agent
CN105037650B (en) * 2015-08-31 2018-06-26 四川大学 Application of the trimethylolpropane trimethacrylate in polycarboxylate water-reducer is prepared
CN105542092B (en) * 2016-01-20 2018-01-05 南京师范大学 The method that normal temperature synthesizes spacetabs type high-slump-retentionpolycarboxylate polycarboxylate water reducer
CN105693948A (en) * 2016-03-22 2016-06-22 广东乐尔康生物科技股份有限公司 Preparation method of green and environment-friendly, and high-stability polycarboxylic acid water reducing agent mother liquid
CN105837762A (en) * 2016-05-30 2016-08-10 江苏名和集团有限公司 Polycarboxylate superplasticizer synthesized at normal temperature and preparation method thereof
CN106065051A (en) * 2016-06-08 2016-11-02 江苏新光环保工程有限公司 A kind of normal temperature preparation method of polycarboxylic acid series high efficiency water reducing agent
CN107759743A (en) * 2016-08-22 2018-03-06 北京时代思动科技有限公司 A kind of diminishing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof
CN106279565A (en) * 2016-08-26 2017-01-04 石家庄市海森化工有限公司 A kind of two excitation system produces solid polycarboxylic acid water reducing agent and preparation method thereof
CN106317343A (en) * 2016-08-29 2017-01-11 东盟营造工程有限公司 Water-reducing agent for polycarboxylate concrete and preparation and application thereof
CN106380552A (en) * 2016-09-29 2017-02-08 湖北工业大学 High-adaptability polycarboxylic acid water reducing agent master batch
CN107325235A (en) * 2017-07-14 2017-11-07 贵州禹华建材科技有限公司 One kind protects the sustained-release polycarboxylic water reducer normal temperature synthesis technique that collapses
CN110540620A (en) * 2019-01-09 2019-12-06 咸阳鸿鑫建材有限公司 polycarboxylate superplasticizer and preparation method thereof
CN109970924A (en) * 2019-04-08 2019-07-05 四川铁科新型建材有限公司 A kind of room temperature synthesis composite functional polycarboxylate superplasticizer mother liquor and preparation method thereof
CN111909323A (en) * 2019-05-10 2020-11-10 亚泰集团沈阳现代建筑工业有限公司 Normal-temperature synthesis method of polycarboxylate superplasticizer
CN110128603B (en) * 2019-06-11 2021-10-01 云南建投高分子材料有限公司 Method for stably synthesizing polycarboxylate superplasticizer under low-temperature condition
CN110452339A (en) * 2019-07-05 2019-11-15 秦皇岛智勤科技有限公司 Preparation process of polycarboxylate superplasticizer with low-temperature conventional water quality
CN111019059B (en) * 2019-12-12 2022-08-19 甘肃第一建设集团有限责任公司 Polycarboxylate superplasticizer synthesized at normal temperature and synthesis method thereof
CN111154045A (en) * 2019-12-30 2020-05-15 四川恒泽建材有限公司 Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof
CN112574365A (en) * 2020-12-10 2021-03-30 桂林理工大学 Concrete polycarboxylic acid water reducer synthesized at normal temperature and preparation method thereof
CN112920347A (en) * 2021-04-07 2021-06-08 甘肃建投商品混凝土有限公司 Preparation method of C70-based high-strength concrete crushed pebble and crushed stone concrete admixture
CN113402194A (en) * 2021-07-26 2021-09-17 中铁十一局集团桥梁有限公司 Water reducing agent, preparation method thereof and concrete
CN114105513B (en) * 2021-11-22 2022-10-25 云南森博混凝土外加剂有限公司 Alkali-free accelerator and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102286134A (en) * 2011-06-09 2011-12-21 江苏天音化工有限公司 Preparation method for high-performance water reducing agent
CN103172291A (en) * 2012-12-14 2013-06-26 上海东大化学有限公司 Polycarboxylic-acid water reducing agent synthesized at normal temperature, and preparation method and application method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102286134A (en) * 2011-06-09 2011-12-21 江苏天音化工有限公司 Preparation method for high-performance water reducing agent
CN103172291A (en) * 2012-12-14 2013-06-26 上海东大化学有限公司 Polycarboxylic-acid water reducing agent synthesized at normal temperature, and preparation method and application method thereof

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